Azodyestuffs insoluble in water and process of making same



Patented Dec. 26, 1933 AZODYESTUFFS KNSOLUBLE WATER AND- PROCESSOF MAKING SAME Leopold Laska and Bruno Heyn,

the Main, Germany, assignors to Offenbach-on General Aniline Works, Inc.,' New York,'N. Y., a corporation of Delaware No Drawing. Application April 6,1929, Serial 1%.

353,250, and in Germany April 18, 1928 23 Claims.

Our present invention relates'to new azo dyestufis insoluble in water, corresponding probably to the general formula:

wherein R1 means hydrogen or alkyl, R2 hydro l boxylic acid arylide compound of the general formula wherein R1 and R2 have the aforesaid signification. 7

Since the amino-naphthol compounds contain two combining places as shown in the above formula of the dyestuffs, two series of dyestuffs can be obtained according to the combining conditions used.

The 6-amino-2-naphthol-S-carboxylic acid arylide compounds employed as combining components in our process may be prepared by converting the 6-amino-2-n'aphthol-3-carboxylic acids (obtainable by treating 2.6-dihydroxynaphthalene-3-carboxylic acid with ammonia or amines containing at least one reactive hydrogen atom at the nitrogen atom, for instance, methylamine, aniline, methyl-phenylamine etc., and homologs and substitution products of these amines). into the corresponding arylides in the customary manner, for instance, as described in naphthol-3-carboxylic acid or its substitution products. with aromatic amines'in the presence of diluents-and condensing agents.

Our present process is of a peculiar-technical value as it is the first time that the manufacture.

of green monoazo dyestuffs is successful.

The dyestuffs herein describedyield valuable color lakes when mixed with the usual substrata U. S. Patent 1,101,111, by heating the 6-amino-2- or fast dyeings and printings on the fiber when prepared according to the ice-color method.

In order to further illustrate our invention the following examples are given,-but we wish it to be understood that we are not limited to the particular products or reaction conditions mentioned therein.

Example (11) Preparation of the padding solution:

6 grs. of 6-phenylamino-2-hydroxy-naphthalene-3-carboxylic acid anilide are made into a paste with 12 cc. of Turkey red oil of 50% strength and 18 cc. of a caustic soda, solution of 34 Be. The pasteis covered with250 cc; of hot water and dissolved by boiling. Then the whole ismade up to lliter. If the padding goods are not immediately developed after the padding process, 6 cc. of formaldehyde of 30% strength are advantageously added at'about to the padding solution. v

(b) Preparation of the developing solution:

' 1,65 grs. of ortho-chloro aniline are made into a paste with 10 cc. of hot water and'2 cc. of hydro chloric acid of 20 Ben The paste is dissolved by the addition of 40 cc. of cold water. Then the solution is cooled to 5 by means of iceand mixed while stirring with 0,7? grs. of sodium nitrite dis solved in a small quantity of water. After about 15 minutes the diazotizing reaction is finished. The diazo solution is neutralized with whiting, filtered from the'excess thereof and made up to 1 liter. 7 I

.(c) Dyeing process-t i 50 grs. of cotton yarn, unbleached, well boiled and uniformly dehydrated, are treated at 30 with the padding solution described (Sub a) for half an hour while often turning it. Then the yarn is well squeezed out between two rubber rolls and developed, while well turning it, with the neutralized diazo solution prepared according to (b).

. The dyed yarn is rinsed twice or thrice in the cold,

then once hot. Thereafter it is soaped for half an hour with a solution containing per liter 3 grs. of soap and 1 gr. of sodium carbonate and finally it is hot and cold rinsed and dried.

In this manner an olive-green dyeing is obtained. I

The same dyeing results bycarrying out the combination in asolution containing sodium carbonate; A somewhat less pure shade is obtained 7 when the combination is effected inthe presence of acetic acid.- 'In a mineral acid solution the combination yields a bluish red' shade. v i

In an'analogous'manner the dyestuff may prepared in substance.

- The following table exhibits the shades of some 7 dyeings of this kind prepared with diazo solutions which are neutralized with carbonate of lime:

radical of the benzene-, naphthaleneor anthrae cene series, Z being hydrogen or the group Combining component Base to be diazotized Shade 0 6-Phenylamino-2-naphthol-3-carboxy1ic acid lnilide Alpha-naphthylarnine Dark green. 8

Do 4-chloro-o-anisidinel. Do- 5-chloro-o-toluidine. Green. p-nitraniline Olive. m-nitIo-p-toluidine o. m-nitro-o-anisidine Olive-green. o-aminoazotolucne 've. Alpha-aminoanthraquinone Do. Dianisidine Dark green. Alpha-napththylamine Do 2.5-dichloro aniline Bronze. 5-cl1l0ro-o-toluidine Yellowish green. 2.4.5-trichloro aniline Greyish brown. p-nitraniline Olive. p-chloro-o-anisidine Dark green. 5 chloro-o-toluidine Green. p-nitraniline Olive. D0 o-aminoazotoluene. Do. 6-o-Ohloro phenylam1no-2-naphthol-3-carboxy p-nitraniline Do.

Do o-aminoazotoluene- Dark green. G-p-Ghloro phenylamino-2-naphthol-3-carbox Alpha-naphthylamine Do. Do fi-chloro-o-toluidine Yellowish dark green. 'i-chloro-o-anisidine Bluish dark green. p-nitraniline Olive. o-aminoazotoluene Olive-green.

. fi-chloro-o-toluidine Do. 6-N Methyl-phenylammo-Z-naphthol-3-carboxylieacid-anilide o-chloroaniline Green.

D 4-chloroo-anisidine Dark green. D0 5-chloro-o-toluidine- Green. Do p-nitraniline Yellowish olive. Do m-nitro-o-anisidin Yellowishgreen. Dn o-aminoazotoluene Olive-green. 6-Amino-2-naphthol-3-carboxylic acid-p-toluidide o-chloroaniline Brown.

Do V p-nitraniline--- Bronze. Do.-. o-arninoazotoluen Olive-brown.

We wish it to be understood that in the follow- N=N R4, wherein R4 stands for a radical of Claims the term O bi ea s Ve ythe benzene series, which compounds are colored Where Combining 111 Substance 011 a powders, insoluble in water, yielding valuable stratum, especially on the fiber. color lakes and fast dyeings and printings when Since an ob ect of the present invention is to produced on the fiber. p v y u s f d as p pe ti s. 3. The 2.20 dyestuffs of the probable general 5 which dyestufis are insoluble in water and alkaformula: V lies, it is to be understood that the aromatic N=N-RZ nuclei of the general formulae appearing in the appended claims contain no substituents as are OH, 115 known to render organic compounds soluble in water or alkalies and to tend to depreciate the N OONHR; fastness of the dyestuffs to alkalies. Substituents R2 of this kind are, for instance, the sulfonic acid and the carboxylic acid group.

We claim:

'1. A process which comprises combining a compound of the group consisting of diazo-, tetrazoand diazoazo-compounds of the benzene, naphthalene and anthracene series not containing sulfonic or carboxylic acid groups with a 6-amino-2-naphthol-3-carboxylic acid arylide compound of the general formula: 7

OH R1 wherein R1 means hydrogen or alkyl, R2 hydrogen or a radical of the benzene series and R3 a CO-NH-Ra radical of the benzene series.

2.'The azodyestuffs of the probable general formula: V i

r I X wherein R1 means hydrogen or alkyl, R2 hydrogen or a radical of the benzene series,'R3 a radical of the benzene series, one X hydrogen and the otherX the group N=N,RZ,R being a wherein R1 means hydrogen or alkyl, R2 hydrogen or a radical of the benzene series, R3 a radical of the benzene series, R a radical of the ben-' zene-, naphthaleneor anthracene series, Z being hydrogen or the group --l T=N--R4, wherein R4 stands for a radical of the benzene series; which R2NH CONH-Ra wherein R2 and R3 stand for radicals of the benzene series.

5. The azo dyestuffs of the probable general formula:

wherein R stands for a radical ofthe benzene-, naphthaleneor anthracene series, R2 and R3 for radicals of the benzene series, which compounds are greenish powders, insoluble in water, yielding valuable color lakes and fast greenish dyeings and printings when produced on the fiber.

6. The process which comprises combining a diazo compound of the benzene series with a compound of the general formula:

a \N- CONH-Ra Rz wherein R2 and R3 stand for radicals of the benzene series.

"I. The azo dyestuffs of the probable general formula:

N=NR' H OH 'CO-NH-R:

R2 1 wherein R, R2 and R3 stand for radicals of the benzene series, which compounds are greenish powders, insoluble in water, yielding valuable color lakes and fast greenish dyeings and printings when produced on the fiber.

8. A process which comprises combining the diazo compound of 5-chloro-2-amino-toluene with a 6-arylamino-2-naphthol-3-carboxylic acid arylide of the general formula:

Rz-NH oo-NH-R I wherein R2 and R3 stand for radicals of the benzene series. 1

9. The azo dyestuffs of the probable general formula: v

N=--N- or v on ons R2NH o ONHRa wherein R2 and R3 stand for radicals of the benzene series, which compounds are greenish powders, insoluble in water, yielding valuable color lakes and fast greenish dyeings and printings when produced on the fiber.

10. A process which comprises combining the diazo compound of 5-chloro-2-amino-toluenewith a 6-(4 '-tolylamino) -2-naphthol-3-carboxylic acid arylide of the general formula:

HaCONH c 0NHRa wherein R3 means a radical of the benzene series. 11. The azo dyestuffs of the probable general formula 1 wherein R3 stands for a radical of the benzene series, which compounds are greenish powders, insoluble in water, yielding valuable color lakes and fast greenish dyeings and printings when produced on the fiber.

12. A process which comprises combining the diazo [compound of 5-chloro-2-amino-toluene with a 6- (4' -tolyl-amino) -2-na phthol-3-carboxylic acid-2-anisidide of the formula:

13. A process which comprises combining the diazo compound, neutralized with calcium carbonate, of 5-chloro-2-amino-toluene with a 6-(4'- tolyl-amino) -2-naphthol 3 carboxylic acid-2- anisidide of the formula:

' I 0 CH3- 14. The azo dyestuff of the probable formula:

OH HaOONH- oo-NHQ Y CH3 which compound is a green powder, insoluble in water, yielding valuable color, lakes and fast green dyeings and printings when produced on the fiber. 15. The azo' dyestuif of the probable formula:

which compound fast olive-green dyeings and printings when produced on the fiber.

claimed in claim 15.

' LEOPOLD LASKA.

BRUNO HEYN.

is an olive-green powder, insoluble in water, yielding valuable color lakes and 

